DE102009055061A1 - New initiation procedure for the polymerization of (meth) acrylates - Google Patents

Abstract

The present invention relates to a novel polymerization method for (meth) acrylates, in which the polymerization is initiated by isocyanates and special bases with an imine structure. With this new method, which can be used in a targeted manner, it is also possible to produce high molecular weight poly (meth) acrylates, some of which have a narrow molecular weight distribution. In addition, a wide variety of polymer architectures, such as block, star or comb polymers, are available using this new polymerization method.

Description

Field of the invention

The present invention relates to a novel polymerization method for (meth) acrylates in which the polymerization is initiated by isocyanates and special bases having an imine structure. High molecular weight poly (meth) acrylates with partially narrow molecular weight distributions can also be prepared with this new and specifically usable method. In addition, using this new polymerization method, a wide variety of polymer architectures, such as block, star or comb polymers, are available.

The notation (meth) acrylate here means both methacrylate, such as. As methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, such as. As methyl acrylate, ethyl acrylate, etc., as well as mixtures of the two.

State of the art

For the polymerization of (meth) acrylates, a number of polymerization methods are known. Above all, the free radical polymerization is industrially of crucial importance. It is widely used as substance, solution, emulsion or suspension polymerization for the synthesis of poly (meth) acrylates for a wide variety of applications. These include molding compounds, Plexiglas, paint binders, additives or components in adhesives or sealants, to name but a few. The disadvantage of free-radical polymerization, however, is that it has no effect on the polymer architecture, that it can only be functionalized in a very unspecific manner, and that the polymers have a broad molecular weight distribution.

By contrast, high molecular weight and / or narrowly distributed poly (meth) acrylates are available by means of anionic polymerization. Disadvantages of this polymerization, however, are the high demands on the process management z. As regards moisture exclusion or temperature, and the impossibility to realize functional groups on the polymer chain. The same applies to the group transfer of methacrylates, which is of very little importance today.

As living or controlled polymerization methods are suitable in addition to the anionic and modern methods of controlled radical polymerization. Both the molecular weight and the molecular weight distribution are controllable. As a living polymerization, they also allow the targeted construction of polymer architectures such as random copolymers or block copolymer structures.

An example is the RAFT polymerization (reversible addition fragmentation chain transfer polymerization). The mechanism of RAFT polymerization is described in EP 0 910 587 to describe in more detail. Disadvantages of the RAFT polymerization are, in particular, the limited possibility of synthesis of short-chain poly (meth) acrylates or of hybrid systems and the fate of sulfur groups in the polymer.

By contrast, the NMP method (nitroxide mediated polymerization) can only be used to a limited extent for the synthesis of poly (metn) acrylates. This method has major disadvantages with respect to various functional groups and the targeted adjustment of the molecular weight.

The ATRP method (atom transfer radical polymerization) was developed in the 1990s mainly by Prof. Matyjaszewski ( Matyjaszewski et al., J. Am. Chem. Soc., 1995, 117, p. 5614 ; WO 97/18247 ; Science, 1996, 272, p. 866 ). The ATRP yields polymers narrowly distributed in the molecular weight of M _n = 10,000 to 120,000 g / mol. Disadvantage is mainly the use of transition metal catalysts, especially of copper catalysts that can be removed only very expensive or incomplete from the product. In addition, acid groups are disturbing during the polymerization, so that such functionalities can not be realized directly by means of ATRP.

In Okamoto et al (J. of Pol. Sci .: Polymer Chemistry, 12, 1974, pp. 1135-1140) describes the initiation of MMA polymerization with triethylamine and isocyanates. However, this system only results in yields below 20%.

task

The object of the present invention is to provide a novel polymerization method for the polymerization of (meth) acrylates.

In particular, the object is to provide a polymerization method by means of which high molecular weight poly (meth) acrylates with optionally narrow molecular weight distributions in yields greater than 20% can be produced.

In addition, a further object is to provide a polymerization method for (meth) acrylates which is variable and versatile and which leaves no interfering initiator or catalyst residues such as transition metals in the polymer.

Other tasks not explicitly mentioned emerge from the overall context of the following description, claims and examples.

solution

The objects were achieved by a surprisingly found new initiation mechanism, with which a polymerization of vinylic monomers M can be started. In this context, vinylic monomers M are understood as meaning monomers which have a carbon-carbon double bond. As a rule, such monomers can be polymerized free-radically and / or anionically. In this new process, the polymerization of the monomers M is initiated by the presence of a component A and a component B. Component A is an isocyanate or a carbodiimide. Component B is an organic base.

There are two preferred methods for carrying out the initiation. In one, component B is added to a mixture of component A and vinylic monomer M. In the other, component A is added conversely for initiation to a mixture of component B and vinylic monomer M.

Component B is preferably a tertiary organic base, more preferably an organic base having a carbon-nitrogen double bond, or alternatively a trithiocarbonate.

In particular, bases having the following functional groups are suitable for use in the initiation process according to the invention: imines, oxazolines, isoxazolones, thiazolines, amidines, guanidines, carbodiimides, imidazoles or trithiocarbonates.

Imines are compounds which have a (Rx) (Ry) C = N (Rz) groups. The two groups on the carbon atom Rx and Ry and the one group on the nitrogen atom Rz are freely selectable, different or identical to one another and it is also possible that these form one or more cycles. Examples of such imines are 2-methylpyrroline (1), N-benzylidenemethylamine (BMA, (2)) or N-4-methoxybenzylideneaniline (3).

Oxazolines are compounds which have a (Ry) OC (Rx) = N (Rz) group. Also in these compounds, the groups on the carbon atom Rx, the oxygen Ry and the nitrogen atom Rz are each freely selectable, different or identical to each other and it is also possible that these form one or more cycles. Examples of oxazolines are 2-ethyloxazoline (4) and 2-phenyloxazoline (5):

Isoxazolones are compounds having the structural element (6):

Also applies to the two groups on the carbon atom Rx or Ry and the one group on the nitrogen atom Rz of isoxazolones that they can be freely selected and different or identical to each other. It is also possible that these form one or more cycles. An example of such an isoxazolone is 3-phenyl-5-isoxazolone (7):

Thiazolines are compounds having the structural element (8) or (9):

For the groups at the carbon atom Rx, at the sulfur atom Ry, at the second sulfur atom Rx 'and at the nitrogen atom Rz applies that these can be freely selectable and different or identical to each other. It is also possible that these form one or more cycles. Examples of such thiazolines are 2-methylthiazoline (10) or 2-methylmercaptothiazoline (11):

Amidines are compounds with the structural element (12), with guanidines compounds with the structural element (13):

For the groups on the carbon atom Rx, on the nitrogen atom Rz, on the second nitrogen atom Ry and Ry 'and on the third nitrogen atom Rx' and Rx '', it is true that these can be freely selectable and different or identical to one another. It is also possible that these form one or more cycles. Examples of amidines are 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, (14)), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN, (15)) or N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole (PDHI, (16)):

Examples of the guanidines are 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (MTBD, (17)), 1,1,3,3-tetramethylguanidine (TMG, (18)) or N-tert-butyl-1,1,3,3-tetramethylguanidine (19):

The group of carbodiimides are compounds with the structural element (Rz) -N = C = N- (Rz '). For the groups on the nitrogen atoms Rz and Rz 'it is true that they can be chosen freely and be different or identical to one another. It is also possible that these form one or more cycles. An example of carbodiimides is diisopropylcarbodiimide (20):

Additionally usable compounds may be imidazole (21) or 1-methylimidazole (22):

Examples of usable organic bases without C = N bond are trithiocarbonates having the structural element (23):

For the groups at the two sulfur atoms Ry and Ry 'it holds that they can be freely chosen and different or identical to each other. It is also possible that these form one or more cycles. An example of trithiocarbonates is ethylidene trithiocarbonate (24):

The examples of the organic bases are in no way suitable for limiting the invention in any way. Rather, they serve to illustrate the multitude of compounds that can be used according to the invention.

Component A is isocyanates which may be mono-, di- or polyfunctionalized. The formulation isocyanate also includes the chemically equivalent thioisocyanates.

The further functionalities may in one embodiment be a second or further isocyanate groups. In another embodiment, it is also possible that the further functionalities are other functionalities which form stable compounds together with isocyanate groups.

Examples of monofunctional isocyanates are cyclohexyl isocyanate (25), phenyl isocyanate (26) and tert-butyl isocyanate (27). Example of a monofunctional thioisocyanate is phenyl thioisocyanate (28):

Examples of bifunctional isocyanates having two isocyanate groups are 1,6-hexamethylene diisocyanate (HDI, (29)), toluene diisocyanate (TDI, (30)) and isophorone diisocyanate (IPDI, (31)):

Further examples are condensates of these bifunctional isocyanates, in particular trimers of the isocyanates with two isocyanate groups, such as the HDI trimer (32) or the IPDI trimer (33):

In addition, it is also possible to use monofunctional, linear isocyanates, such as dodecyl isocyanate (34) or ethyl isocyanate (35):

As an alternative to the isocyanates and carbodiimides can be used. These are compounds with the structural element (Rz) -N = C = N- (Rz ') according to the structure already described, as was carried out to the usable organic bases. An example of a carbodiimide that can be used in place of isocyanates is diisopropylcarbodiimide (20):

In a particular embodiment of the invention using carbodiimides both components A and B may be identical. In this embodiment, it is also not necessary to add one of the two components with a time delay to the system, so that there is a one-component initiator system in this exception of the embodiment.

In an alternative embodiment, it is also possible that only an adduct is formed from the two components isocyanate and organic base, which in turn can initiate a polymerization. These intermediates are also isolatable, so that they can be used as alternative initiators. An example of such an adduct is the reaction product (36) of two molecules TMG (18) and HDI (29):

The inventive method for initiating a polymerization is basically independent of the polymerization process used. The process for the initiation and the subsequent polymerization can be carried out, for example, in the form of a solution or bulk polymerization.

The polymerization can be carried out in batch mode or continuously. The polymerization can also be carried out over the entire usual temperature spectrum and at super, normal or negative pressure.

A particular aspect of the present invention is that the polymers obtained from the process are obtained in a very broad molecular weight range. These polymers can according to a GPC measurement against a polystyrene standard have a molecular weight between 1000 and 10 000 000 g / mol, in particular between 5000 and 5 000 000 g / mol and more particularly between 10 000 and 2 000 000 g / mol.

The vinylic monomers M are monomers which have a double bond, in particular monomers with double bonds which are free-radically and / or anionically polymerizable. In particular, these are acrylates, methacrylates, styrene, styrene-derived monomers, α-olefins or mixtures of these monomers.

The notation (meth) acrylates is furthermore alkyl esters of acrylic acid and / or methacrylic acid.

In general, the monomers are selected from the group of alkyl (meth) acrylates of straight-chain, branched or cycloaliphatic alcohols having 1 to 40 carbon atoms, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth ) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate which may each have unsubstituted or 1-4-substituted aryl radicals; other aromatic substituted (meth) acrylates such as naphthyl (meth) acrylate; Mono (meth) acrylates of ethers, polyethylene glycols, polypropylene glycols or mixtures thereof with 5-80 carbon atoms, such as, for example, tetrahydrofurfuryl methacrylate, methoxy (m) ethoxyethyl methacrylate, 1-butoxypropyl methacrylate, cyclohexyl-oxymethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2- Ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate, poly (ethylene glycol) methyl ether (meth) acrylate and poly (propylene glycol) -methyl ether (meth) acrylate, together.

In addition to the (meth) acrylates set out above, it is also possible to polymerize further unsaturated monomers. These include, but are not limited to, 1-alkenes such as 1-hexene, 1-heptene, branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene, acrylonitrile , Vinyl esters such. For example, vinyl acetate, styrene, substituted styrenes having an alkyl substituent on the vinyl group, such as. For example, α-methylstyrene and α-ethylstyrene, substituted styrenes having one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, heterocyclic compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4 vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 2-methyl-1-vinylimidazole, vinloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles, vinyloxazoles and isoprenyl ethers. Further monomers are, for example, vinylpiperidine, 1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpirrolidone, N-vinylpirrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, hydrogenated vinylthiazoles and hydrogenated vinyl oxazoles.

The polymers produced by the novel process can be used in many applications. These include, but are not limited to, the invention in any form, acrylic, molding, raw materials for other injection or extrusion applications, films, mirror films, packaging films, optical films laminates, laminate adhesives, foams, sealants, foamed materials for packaging, synthetic fibers , Composite materials, paint binders, Paint additives, such as dispersing additives or particles for scratch-resistant coatings, primers, binders for adhesives, hot-melt adhesives, pressure-sensitive adhesives, reactive adhesives or sealants, heat sealing lacquers, packaging materials, dental materials, bone cement, contact lenses, spectacle lenses, other lenses, for example. In industrial applications, road markings, floor coatings, plastisols, underbody coatings for vehicles, insulation materials, materials for use in galenics, drug delivery matrices, oil additives such as flow improvers, polymer additives such as impact modifiers, compatibilizers or flow improvers, staple fiber additives, particles in cosmetic applications or as a raw material for the production of porous forms.

Examples

The weight average molecular weights of the polymers of Examples 1 to 38 were determined by GPC (gel permeation chromatography). The measurements were carried out with a PL-GPC 50 Plus from Polymer Laboratories Inc. at 40 ° C. in THF against a polystyrene standard. The measuring limit for M _w is approx. 400 000 g / mol.

The weight-average molecular weights of the polymers from Examples 43 to 48 were determined by GPC (gel permeation chromatography) based on DIN 55672-1 certainly. The measurements were carried out with a GPC from Polymer Laboratories Inc. at an oven temperature of 35 ° C., in THF, for a running time of 48 minutes and against a polystyrene standard. The measurement limit for M _w is over 15,000,000 g / mol.

The determination of the yields was carried out by weighing the isolated polymer after drying in a vacuum drying oven at 60 ° C and 20 mbar to constant weight.

General implementing rule for examples 1 to 21

2.5 g (2.65 mL, 25 mmol) of methyl methacrylate (MMA), the base (used base + molar ratio to the MMA: see Table 1) and, optionally, a solvent (3 mL, see table) are placed in a 25 mL round bottom flask. submitted and stirred at 25 ° C. With external cooling with an ice-salt mixture, the isocyanate (isocyanate used + molar ratio to the MMA: see Table 1) is added thereto with constant stirring. After a reaction time t (see Table 1) with stirring and at 25 ° C, the resulting mixture is dissolved in 15 ml of chloroform and filtered. The solution is then precipitated by means of dropping for purification in 300 ml of ice-cooled methanol. The PMMA precipitates as a white solid, is filtered off, washed three times with methanol and dried in a vacuum oven at 60 ° C and 20 mbar to constant mass. Results see Table 1.

General implementing rule for examples 22 to 27

2.5 g (2.65 mL, 25 mmol) of methyl methacrylate (MMA) and the base (base used + molar ratio to the MMA: see Table 1) are introduced into a 25 mL round bottom flask and stirred at 25.degree. To the solution, the isocyanate (isocyanate used + molar ratio to the MMA: see Table 2) is added and heated under reflux. This usually corresponds to a temperature of the solution of 90 ° C. After a time t (see Table 2) stirring at the boiling point of the solution, there is an increasing increase in viscosity. The solution is cooled, the viscous oil is dissolved in 10 ml of chloroform, precipitated in 300 ml of ice-cooled n-hexane by means of dropwise addition, and the solid obtained is filtered off. The resulting PMMA is washed several times with n-hexane and dried in a vacuum oven at 60 ° C and 20 mbar to constant mass.

From the filtrate of the precipitation, n-hexane can be distilled off and the residue obtained from it can be used again for the polymerization. It is to be expected in this type of purification with a mass loss of 5% to 27% of the system base / isocyanate. Results see Table 2.

General implementing rule for examples 28 to 32

The base (base used + molar ratio to MMA: see Table 3) is dissolved in 3 mL CHCl ₃ in a 25 mL round bottom flask. To the solution, 2.5 g (2.65 mL, 25 mmol) of MMA and the isocyanate (isocyanate used + molar ratio to MMA: see Table 3) are added and heated to reflux. This usually corresponds to a temperature of the solution of 90 ° C. After a time t (see Table 3) stirring at the boiling point of the solution, there is an increasing increase in viscosity. The solution is cooled, the viscous oil dissolved in 10 ml of chloroform, precipitated in 300 ml of ice-cooled n-hexane by dropwise addition and the the solid filtered off. The resulting PMMA is washed several times with n-hexane and dried in a vacuum oven at 60 ° C and 20 mbar to constant mass.

From the filtrate of the precipitation, n-hexane can be distilled off and the residue obtained from it can be used again for the polymerization. It is to be expected in this type of purification with a mass loss of 5% to 27% of the system base / isocyanate. Results see Table 3.

General procedure for Examples 33 to 36 and Comparative Examples V1 to V4

In a 25 mL round bottom flask is mixture A (for composition, see Table 4). submitted and stirred at 25 ° C. With external cooling with an ice-salt mixture, mixture B is added thereto with constant stirring. After 18 h with stirring at 25 ° C, the resulting mixture is dissolved in 15 ml of chloroform and filtered. The solution is then precipitated by means of dropping for purification in 300 ml of ice-cooled methanol. Resulting PMMA is obtained as a white solid, is filtered off, washed three times with methanol and dried in a vacuum drying oven at 60 ° C and 20 mbar to constant mass. This white solid can only be PMMA. Detection takes place by means of ¹ H-NMR spectroscopy. The presence of PMMA is evidence of successful polymerization. A separate characterization of the incurred polymers did not take place in this case. In Examples 39 to 42 and in Comparative Examples V1 to V4, 2.5 g (2.65 mL, 25 mmol) of methyl methacrylate are used in each case. This corresponds to 6 molar equivalents, to which in each case 1 molar equivalent of hexamethylene diisocyanate (HDI, 29) and 1 molar equivalent of 1,1,3,3-tetramethylguanidine (TMG, 18) or 1,8-diazabicyclo [5.4.0] undec -7-en (DBU, 14). For results, see Table 4.

General implementing rule for examples 37 to 42

2.5 g (2.65 mL, 25 mmol) of methyl methacrylate (MMA) and 1,1,3,3-tetramethylguanidine (TMG, (18), molar ratio to MMA: see Table 5) are introduced into a 25 mL round bottom flask and stirred at 25 ° C. With external cooling with an ice-salt mixture, 1.6-hexamethylene diisocyanate (HDI, (29), molar ratio to MMA: see Table 5) is added thereto with constant stirring. After 7 days with stirring at 25 ° C, the resulting mixture is dissolved in 15 ml of chloroform and filtered. The solution is then precipitated by means of dropwise addition in 300 ml of ice-cooled hexane for purification. The PMMA precipitates as a white solid, is filtered off, washed three times with hexane and dried in a vacuum oven at 60 ° C and 20 mbar to constant mass. For results see Table 5. Table 1 Ex. base isocyanate MMA / Base / isocyanate t [h] Solvent / c _MMA [mol / L] M [g / mol] Yield PMMA [%] 1 (14) (29) 6/1/1 18 CHCl ₃ / 2.80 112900 69 2 (35) 2/1/1 18 substance 267000 53 3 (34) 6/1/1 48 substance 209000 51 4 (25) 6/1/1 18 substance 141000 28 5 (15) (29) 6/1/1 34 CHCl ₃ / 2.83 > 400000 60 6 (34) 6/1/1 48 substance > 400000 73 7 (18) (25) 2/1/1 18 substance nb 56 8th (29) 2/2/1 18 substance nb 89 9 (19) (29) 1/1/1 18 substance > 400000 30 10 (25) 1/1/2 18 substance 13000 24 11 (17) (29) 6/1/1 18 substance 66000 64 12 (1) (29) 2/1/1 18 substance 79000 80 13 (35) 6/1/2 18 substance 106000 29 14 (10) (29) 2/1/1 20 substance 161000 25 15 (11) (29) 2/1/1 18 substance 107000 100 16 6/1/1 18 substance 203000 82 17 25/1/1 18 substance > 400000 73 18 3/1/1 62 Hexane / 2.02 63000 83 19 (7) (29) 6/1/1 67 CHCl ₃ / 3.00 113100 65 20 6/1/1 20 THF / 2.21 77800 57 21 (22) (29) 2/1/1 24 substance 229000 58 Table 2 Ex. base isocyanate MMA / Base / isocyanate t [h] M [g / mol] Yield PMMA [%] 22 (2) (29) 2/1/1 6 167000 69 23 (3) (29) 6/1/1 6 229000 47 24 (4) (29) 2/1/1 6 88000 74 25 (26) 2/1/1 6 > 400000 23 26 (20) (29) 2/1/1 3 63000 77 27 - 2.1 30 19000 12 Table 3 Ex. base isocyanate MMA / Base / isocyanate t [h] Solvent / c _MMA [mol / L] M _w [g / mol] Yield PMMA [%] 28 (2) (29) 6/1/1 25 CHCl ₃ / 3.66 nb 23 29 (5) (29) 6/1/1 10 CHCl ₃ / 2.82 > 400000 75 30 (26) 6/1/1 10 CHCl ₃ / 3.76 > 400000 46 31 (24) (26) 2/1/1 54 CHCl ₃ / 2.60 > 400000 18 32 (22) (29) 2/1/1 71 CHCl ₃ / 2.66 nb 24 Table 4 Ex. Mixture A Mixture B polymerization V1 HDI (29) / MMA - No V2 DBU (14) / MMA - No V3 DBU (14) / HDI (29) MMA No 33 DBU (14) / MMA HDI (29) Yes 34 MMA / HDI (29) DBU (14) Yes V4 TMG (18) / HDI (29) MMA No 35 TMG (18) / MMA HDI (29) Yes 36 MMA / HDI (29) TMG (18) Yes Table 5 Ex. MMA / TGM (18) / HDI (29) M _w [g / mol] 37 2/1/1 1 170000 38 6/1/1 2 940000 39 10/1/1 2 270 000 40 14/1/1 2 670 000 41 20/1/1 2 530 000 42 40/1/1 4 220 000

Examples 1 to 25 in Table 1 show that components A and B according to the invention can be used in many different ways, sometimes even at room temperature in solution or as initiators for methacrylates.

Examples 26 to 32 (Table 2) again show combinations of components A and B which can be used at elevated temperatures in substance as initiators. Examples 33 to 38 (Table 3) show corresponding combinations in solution at higher temperatures.

Example 20 is a system in which components A and B are an identical carbodiimide added in one batch.

In Examples 23 and 24, a trithiocarbonate was used as the base.

Examples 39 to 42 (Table 4) show that the process according to the invention for initiating polymerization functions in cases where the monomer and component A or B are initially charged and the other component is added subsequently. The initiation does not work if either component A (Comparative Example C2) or Component B (Comparative Example C1) are missing. Also, initiation does not always work when components A and B are charged and the monomer (s) are added to this mixture (Comparative Examples V3 and V4). An exception to this is, for example, the initiation of Example 32.

Examples 43 to 48 are suitable for demonstrating that, in particular, particularly high molecular weights can be achieved with the process according to the invention.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0910587 [0006]
• WO 97/18247 [0008]

Cited non-patent literature

• Matyjaszewski et al., J. Am. Chem. Soc., 1995, 117, p. 5614 [0008]
• Science, 1996, 272, p. 866 [0008]
• Okamoto et al (J. of Pol Sci .: Polymer Chemistry, 12, 1974, pp. 1135-1140) [0009]
• DIN 55672-1 [0050]

Claims (18)

A process for initiating a polymerization, characterized in that the polymerization of a vinylic monomer M with a component A and a component B is initiated, that component A is an isocyanate or a carbodiimide, that component B is a is organic base, and that component A and component B are added separately to the monomer M. A method according to claim 1, characterized in that for the initiation of the polymerization to a mixture of component A and a vinylic monomer M component B is added. A process according to claim 1, characterized in that component A is added to initiate the polymerization to a mixture of component B and a vinylic monomer M. Process according to at least one of Claims 1 to 3, characterized in that component A is dodecyl isocyanate, ethyl isocyanate, 1,6-hexamethylene diisocyanate (HDI), an HDI trimer, cyclohexyl isocyanate, tert-butyl isocyanate, phenyl isocyanate, toluenediisocyanate (TDI ), Isophorone diisocyanate (IPDI) or an IPDI trimer. Process according to at least one of Claims 1 to 4, characterized in that component B is a tertiary organic base, preferably an organic base which has a carbon-nitrogen double bond, or a trithiocarbonate. Process according to claim 5, characterized in that the base is an imine. A process according to claim 5, characterized in that the base is an oxazoline or an isoxazolone. Process according to claim 5, characterized in that the base is a thiazoline. A process according to claim 5, characterized in that the base is an amidine or a guanidine. Process according to claim 5, characterized in that the base is a carbodiimide. Process according to claim 5, characterized in that the base is an imidazole. Process according to at least one of the preceding claims, characterized in that the polymerization is carried out as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, miniemulsion polymerization or microemulsion polymerization. Process according to at least one of the preceding claims, characterized in that the isocyanate is a difunctional isocyanate. Method according to at least one of the preceding claims, characterized in that the polymer obtained from the process in a GPC measurement against a polystyrene standard has a weight-average molecular weight between 5000 and 10 000 000 g / mol. Process according to at least one of the preceding claims, characterized in that the vinylic monomers M are acrylates, methacrylates, styrene, styrene-derived monomers, α-olefins or mixtures of these monomers. A process for initiating a polymerization, characterized in that the polymerization of a vinylic monomer M is initiated with a carbodiimide. A method according to claim 16, characterized in that the polymer obtained from the process in a GPC measurement against a polystyrene standard has a molecular weight between 5000 and 10 000 000 g / mol. Process according to one of Claims 16 or 17, characterized in that the vinylic monomers M are acrylates, methacrylates, styrene, styrene-derived monomers, α-olefins or mixtures of these monomers.